US4127415A - Aluminum borophosphate glass compositions - Google Patents

Aluminum borophosphate glass compositions Download PDF

Info

Publication number
US4127415A
US4127415A US05/773,525 US77352577A US4127415A US 4127415 A US4127415 A US 4127415A US 77352577 A US77352577 A US 77352577A US 4127415 A US4127415 A US 4127415A
Authority
US
United States
Prior art keywords
sub
glass
mole percent
glasses
compositions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
US05/773,525
Inventor
Carr L. W. Quackenbush
Andrew G. Kolbeck
Richard M. Klein
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Verizon Laboratories Inc
Original Assignee
GTE Laboratories Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by GTE Laboratories Inc filed Critical GTE Laboratories Inc
Priority to US05/773,525 priority Critical patent/US4127415A/en
Priority to GB7567/78A priority patent/GB1593232A/en
Priority to DE19782808647 priority patent/DE2808647A1/en
Priority to CA297,993A priority patent/CA1101895A/en
Priority to JP2288478A priority patent/JPS53109513A/en
Application granted granted Critical
Publication of US4127415A publication Critical patent/US4127415A/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00Glass compositions
    • C03C3/12Silica-free oxide glass compositions
    • C03C3/16Silica-free oxide glass compositions containing phosphorus
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00Fibre or filament compositions
    • C03C13/04Fibre optics, e.g. core and clad fibre compositions
    • C03C13/045Silica-containing oxide glass compositions
    • C03C13/046Multicomponent glass compositions
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C13/00Fibre or filament compositions
    • C03C13/04Fibre optics, e.g. core and clad fibre compositions
    • C03C13/048Silica-free oxide glass compositions

Definitions

  • This invention relates to novel glass compositions formed from oxides of aluminum, boron and phosphorous.
  • glass compositions exhibit a wide variety of physical characteristics including optical properties, electrical properties, chemical properties, solubility for modifiers and heat stability which enables the practitioner to choose a particular glass to fit his needs.
  • glass compositions have limited desirable physical characteristics so that the practioner must provide some means for ameliorating the poor physical properties of the composition in order to take advantage of the desired properties which the glass composition provides.
  • most silicate glasses which have relatively high annealing temperatures also generally have low thermal expansion coefficients.
  • Aluminum borophosphate glass compositions are known in the art.
  • U.S. Pat. No. 3,519,445 discloses an aluminum borophosphate glass-ceramic composition which is disclosed to contain 50 to 80 weight percent P 2 O 5 .
  • the composition is formed in open silica crucibles at 1500°-1650° C. and therefore contains silica in the composition which is derived from the crucible.
  • Volf in Technical Glasses, pages 401-402, SNTL Publishers, Prague and Sir Isaac Pitman, London (1961) discloses aluminum borophosphate glasses containing 10 to 30 mole percent of mixtures of alkali or alkaline earth modifiers which are required for homogeneous glasses. Dale et al., J. Soc. Glass Technology, Vol.
  • glass compositions which provide a wide variety of desirable physical properties. Furthermore, it would be desirable to provide such glass compositions to which can be added modifiers to improve a desired physical characteristic of the glass without degrading other physical characteristics of the glass.
  • This invention provides novel ternary glass compositions enclosed by the iso-compositions lines, 2 and 18 mole percent P 2 O 5 , 30 and 70 mole percent Al 2 O 3 and 20 and 60 mole percent B 2 O 3 .
  • the glasses can be modified, if desired by the addition of a wide variety of oxides with the modifier levels allowable being dependent upon the specific modifier composition being added.
  • the glass compositions are characterized by high electrical resistivities, refractive indices of about 1.5 coupled with low optical dispersion, high ultraviolet transparency, high solubility for rare earths, high glass transition temperatures, good solarization resistance and relatively constant thermal expansion coefficients over both a range of refractive indices and glass transition temperatures.
  • the combination of good physical characteristics of these glasses permit their use in large numbers of commercial applications, such as in discharge lamps with luminescent glass envelopes, optical fibers, electrical insulators and optical components.
  • the glass compositions are prepared by blending and sometimes calcining sources of Al 2 O 3 , P 2 O 5 and B 2 O 3 in a crucible such as platinum or alumina.
  • the concentration of reactants employed is such as to obtain a glass composition within the ranges set forth above taking into account vaporization losses during heating.
  • the reactants are heated to their melting temperatures, usually between about 1450° C. and 1800° C. to obtain a melt which is cooled to form the glass.
  • the aluminum borophosphate glasses of this invention are formed in a manner so that vaporization of the glass forming constituents, particularly P 2 O 5 is controlled.
  • Materials which are sources of Al 2 O 3 , B 2 O 3 and P 2 O 5 are blended, calcined if desired and preferably melted in a crucible which does not dissolve in the glass composition or the precursor of the glass composition.
  • Normal melting temperatures range between about 1450° C. and 1800° C., preferably between about 1500° C. and 1650° C., depending upon the specific glass composition being formed.
  • Normal seed-free firing time is between about 0.25 and 4.0 hours, preferably between about 1.0 and 2.0 hours. It is preferred to maintain minimum firing times in order to reduce vaporization of the glass-forming constituents.
  • Representative suitable crucible materials include platinum, platinum/rhodium alloys and aluminum oxide.
  • P 2 O 5 is the most volatile glass-forming constituent, it can be added in concentrations in excess of the desired final concentration in the glass composition.
  • the P 2 O 5 is added to the crucible in the form of a refractory compound such as AlPO 4 , BPO 4 , AlP 3 O 9 , or refractory modifying cation phosphates such as Mg 2 P 2 O 7 , Ca 3 (PO 4 ) 2 , ZrP 2 O 7 or the like.
  • a refractory compound such as AlPO 4 , BPO 4 , AlP 3 O 9 , or refractory modifying cation phosphates such as Mg 2 P 2 O 7 , Ca 3 (PO 4 ) 2 , ZrP 2 O 7 or the like.
  • the glass compositions contain from 2 to 18 mole percent P 2 O 5 , from 30 to 70 mole percent Al 2 O 3 and from 20 to 60 mole percent B 2 O 3 .
  • the ternary glass composition can contain oxide modifiers including SiO 2 , MgO, CaO, TiO 2 , ZrO 2 , Na 2 O, CdO, ZnO, SnO 2 , Tb 2 O 3 , Eu 2 O 3 , Nd 2 O 3 , CeO 2 and the like.
  • the rare earth oxides particularly Tb 2 O 3 , Eu 2 O 3 , Nd 2 O 3 or the like are employed in concentrations up to about 35 weight percent based upon the weight of the ternary glass composition in order to vary the fluorescent output.
  • Zirconia is employed in concentrations of between about 5 and 20 mole percent based upon the ternary glass composition in order to vary glass transition temperature.
  • Silica in concentrations up to about 40 mole percent provides increased resistance to devitrification of the aluminum borophosphate glasses.
  • other specific modifiers or combinations of modifiers can be used to effect other changes in glass properties.
  • Representative sources of P 2 O 5 are AlPO 4 , BPO 4 , AlP 2 O 9 or refractory modifying cation sources such as Mg 2 P 2 O 7 , Ca 3 (PO 4 ) 2 or ZrP 2 O 7 .
  • Representative sources of Al 2 O 3 are Al 2 O 3 , AlPO 4 , AlP 3 O 9 and modifying cation aluminates such as MgAl 2 O 4 .
  • Representative sources of B 2 O 3 are BPO 4 , B 2 O 3 or modifying cation borates such as Mg 3 B 2 O 6 .
  • the glass compositions of this invention are stable against degradation by water as are the conventional multicomponent soda-lime silicate glasses even though both B 2 O 3 and P 2 O 5 in their pure states are strongly deliquescent.
  • the glass transition temperature, (T g which is about equal to the annealing temperature and is a measure of the approximate upper use temperature) for many compositions in the aluminum borophosphate system can be in the range of 700°-820° C.
  • T g which is about equal to the annealing temperature and is a measure of the approximate upper use temperature
  • T g is about 815° C.
  • additions of ZrO 2 can increase T g by up to 100° C.
  • most conventional silicate glasses have annealing temperatures substantially lower than the new glasses; the exceptions are aluminosilicate glasses for which T g has about the same range as the aluminum borophosphates, and fused silica, for which T g is 1000°-1100° C.
  • the aluminum borophosphate glasses also have high electrical reisitivities, with values at 250° C. of over 10 15 ohm cm.
  • the only previously known glasses having comparable resistivities are the calcium boroaluminates where values at 250° C. of up to 10 16 ohm cm have been reported.
  • the optical properties of the aluminum borophosphate glasses are also unusual. Resistance to solarization by x-rays is good in comparison with soda-lime-silica glass. The average decrease in transmission between solarized and unsolarized samples over the wavelength range 300-700 nm is 16% for the aluminum borophosphate glass and 30% for soda-lime glass.
  • Refractive index ranges between 1.47 and 1.58 with optical dispersion, given as the ⁇ -value, between 48 and 71 (where a high ⁇ -value represents a low optical dispersion).
  • the ranges for these two parameters place the new glasses in an advantageous position for optical applications.
  • the ultraviolet cutoff of certain compositions in the aluminum borophosphate system occurs at about 190nm provided that special preparation techniques are used to ensure that low impurity levels are maintained.
  • the new glasses are more transparent at ultraviolet wavelengths than any conventional glasses except fused silica. This feature, coupled with an observed high solubility for rare earth modifiers (which fused silica does not display) and their good solarization resistance, is particularly favorable for luminescent and discharge lamp applications.
  • the aluminum borophosphate glasses also show unusual capabilities for independent property control.
  • the isoproperty contour lines for refractive index and thermal expansion coefficient are not parallel in a large area of the low phosphate glass-forming region.
  • refractive index can be adjusted while retaining a constant thermal expansion coefficient, which is a particularly favorable feature for applications such as optical fibers.
  • the glasses of this invention have refractive indices between 1.47 and 1.58, densities between 2.1 and 2.7 gm/cm 3 and thermal expansion coefficients between about 26 and 55 ⁇ 10 -7 /° C.
  • This example illustrates the method of making the aluminum borophosphate glasses of this invention.
  • the glass compositions as shown in Table I glass compositions of varying P 2 O 5 , Al 2 O 3 and B 2 O 3 content, were made from the reactants shown.
  • the difference between the relative concentrations of the P 2 O 5 , Al 2 O 3 and B 2 O 3 in the reactants and the final compositions is due to vaporization losses or solution of alumina from the crucible wall.
  • the reactants were weighed and blended and melted in a platinum or aluminum oxide crucible at the temperatures and for the times shown in Table I. In some instances, the reactants were calcined between 300° and 950° C.
  • This example illustrates the method of making the aluminum borophosphate glasses of this invention containing oxide modifiers.
  • modified glass compositions were made by the method described in Example I except that they include modifying oxides.
  • the reactants, modifiers, melt temperature and time of heating are shown in Table III.

Abstract

Novel glass compositions are provided which are enclosed by the iso-composition lines, 2 and 18 mole percent P2 O5, 30 and 70 mole percent Al2 O3 and 20 and 60 mole percent B2 O3. The compositions can contain the usual oxide modifiers. These composition are characterized by refractive indices between about 1.47 and 1.58, densities between about 2.1 and 2.7 gm/cm3, thermal expansion coefficients between about 26 × 17-7 /C° and 55 × 10-7 /C°, and glass transition points of between about 600 and 820° C.

Description

BACKGROUND OF THE INVENTION
This invention relates to novel glass compositions formed from oxides of aluminum, boron and phosphorous.
A large number of oxide systems, particularly those including silicon have been utilized to form glass compositions. As is well known, glasses exhibit a wide variety of physical characteristics including optical properties, electrical properties, chemical properties, solubility for modifiers and heat stability which enables the practitioner to choose a particular glass to fit his needs. Usually, glass compositions have limited desirable physical characteristics so that the practioner must provide some means for ameliorating the poor physical properties of the composition in order to take advantage of the desired properties which the glass composition provides. For example, most silicate glasses which have relatively high annealing temperatures also generally have low thermal expansion coefficients.
Aluminum borophosphate glass compositions are known in the art. For example, U.S. Pat. No. 3,519,445 discloses an aluminum borophosphate glass-ceramic composition which is disclosed to contain 50 to 80 weight percent P2 O5. The composition is formed in open silica crucibles at 1500°-1650° C. and therefore contains silica in the composition which is derived from the crucible. Volf in Technical Glasses, pages 401-402, SNTL Publishers, Prague and Sir Isaac Pitman, London (1961) discloses aluminum borophosphate glasses containing 10 to 30 mole percent of mixtures of alkali or alkaline earth modifiers which are required for homogeneous glasses. Dale et al., J. Soc. Glass Technology, Vol. 35, pages 185-192 (1952) disclose aluminum borophosphate glasses containing low concentrations of P2 O5 and containing up to about 30 mole percent of mixture of alkaline earth modifiers, e.g. MgO and CaO which are required to form homogeneous glasses.
It would be desirable to provide glass compositions which provide a wide variety of desirable physical properties. Furthermore, it would be desirable to provide such glass compositions to which can be added modifiers to improve a desired physical characteristic of the glass without degrading other physical characteristics of the glass.
SUMMARY OF THE INVENTION
This invention provides novel ternary glass compositions enclosed by the iso-compositions lines, 2 and 18 mole percent P2 O5, 30 and 70 mole percent Al2 O3 and 20 and 60 mole percent B2 O3. The glasses can be modified, if desired by the addition of a wide variety of oxides with the modifier levels allowable being dependent upon the specific modifier composition being added. The glass compositions are characterized by high electrical resistivities, refractive indices of about 1.5 coupled with low optical dispersion, high ultraviolet transparency, high solubility for rare earths, high glass transition temperatures, good solarization resistance and relatively constant thermal expansion coefficients over both a range of refractive indices and glass transition temperatures. The combination of good physical characteristics of these glasses permit their use in large numbers of commercial applications, such as in discharge lamps with luminescent glass envelopes, optical fibers, electrical insulators and optical components. The glass compositions are prepared by blending and sometimes calcining sources of Al2 O3, P2 O5 and B2 O3 in a crucible such as platinum or alumina. The concentration of reactants employed is such as to obtain a glass composition within the ranges set forth above taking into account vaporization losses during heating. The reactants are heated to their melting temperatures, usually between about 1450° C. and 1800° C. to obtain a melt which is cooled to form the glass.
DESCRIPTION OF SPECIFIC EMBODIMENTS
The aluminum borophosphate glasses of this invention are formed in a manner so that vaporization of the glass forming constituents, particularly P2 O5 is controlled. Materials which are sources of Al2 O3, B2 O3 and P2 O5 are blended, calcined if desired and preferably melted in a crucible which does not dissolve in the glass composition or the precursor of the glass composition. Normal melting temperatures range between about 1450° C. and 1800° C., preferably between about 1500° C. and 1650° C., depending upon the specific glass composition being formed. Normal seed-free firing time is between about 0.25 and 4.0 hours, preferably between about 1.0 and 2.0 hours. It is preferred to maintain minimum firing times in order to reduce vaporization of the glass-forming constituents. Representative suitable crucible materials include platinum, platinum/rhodium alloys and aluminum oxide.
Since P2 O5 is the most volatile glass-forming constituent, it can be added in concentrations in excess of the desired final concentration in the glass composition. Alternatively and preferably, the P2 O5 is added to the crucible in the form of a refractory compound such as AlPO4, BPO4, AlP3 O9, or refractory modifying cation phosphates such as Mg2 P2 O7, Ca3 (PO4)2, ZrP2 O7 or the like. By adding P2 O5 as a refractory compound, improved control of the final glass composition is attained. After substantially complete reaction of the reactants is obtained in the melt, it is cooled in any conventional manner such as by air cooling or by cooling between steel plates to obtain the final amorphous glass composition.
As set forth above, the glass compositions contain from 2 to 18 mole percent P2 O5, from 30 to 70 mole percent Al2 O3 and from 20 to 60 mole percent B2 O3. In addition, the ternary glass composition can contain oxide modifiers including SiO2, MgO, CaO, TiO2, ZrO2, Na2 O, CdO, ZnO, SnO2, Tb2 O3, Eu2 O3, Nd2 O3, CeO2 and the like. The rare earth oxides particularly Tb2 O3, Eu2 O3, Nd2 O3 or the like are employed in concentrations up to about 35 weight percent based upon the weight of the ternary glass composition in order to vary the fluorescent output. Zirconia is employed in concentrations of between about 5 and 20 mole percent based upon the ternary glass composition in order to vary glass transition temperature. Silica in concentrations up to about 40 mole percent provides increased resistance to devitrification of the aluminum borophosphate glasses. In a similar way other specific modifiers or combinations of modifiers can be used to effect other changes in glass properties.
Representative sources of P2 O5 are AlPO4, BPO4, AlP2 O9 or refractory modifying cation sources such as Mg2 P2 O7, Ca3 (PO4)2 or ZrP2 O7. Representative sources of Al2 O3 are Al2 O3, AlPO4, AlP3 O9 and modifying cation aluminates such as MgAl2 O4. Representative sources of B2 O3 are BPO4, B2 O3 or modifying cation borates such as Mg3 B2 O6.
The glass compositions of this invention are stable against degradation by water as are the conventional multicomponent soda-lime silicate glasses even though both B2 O3 and P2 O5 in their pure states are strongly deliquescent. In addition to those properties of aluminum borophosphate glasses which are broadly similar to conventional silicate materials, there are other properties of the new glasses which are unusual. An important example is their refractory characteristics. For instance, the glass transition temperature, (Tg which is about equal to the annealing temperature and is a measure of the approximate upper use temperature) for many compositions in the aluminum borophosphate system can be in the range of 700°-820° C. For compositions in the high alumina corner of the disclosed glass-forming region (e.g. 65m% Al2 O3 -11 P2 O5 -24 B2 O3) Tg is about 815° C. In addition, it has been found that for selected compositions additions of ZrO2 (ca 5-10m%) can increase Tg by up to 100° C. For comparison, most conventional silicate glasses have annealing temperatures substantially lower than the new glasses; the exceptions are aluminosilicate glasses for which Tg has about the same range as the aluminum borophosphates, and fused silica, for which Tg is 1000°-1100° C. The aluminum borophosphate glasses also have high electrical reisitivities, with values at 250° C. of over 1015 ohm cm. The only previously known glasses having comparable resistivities are the calcium boroaluminates where values at 250° C. of up to 1016 ohm cm have been reported. The optical properties of the aluminum borophosphate glasses are also unusual. Resistance to solarization by x-rays is good in comparison with soda-lime-silica glass. The average decrease in transmission between solarized and unsolarized samples over the wavelength range 300-700 nm is 16% for the aluminum borophosphate glass and 30% for soda-lime glass. Refractive index ranges between 1.47 and 1.58 with optical dispersion, given as the ν-value, between 48 and 71 (where a high ν-value represents a low optical dispersion). Because most silicates have higher refractive indices and smaller ν-value (i.e. higher dispersions), the ranges for these two parameters place the new glasses in an advantageous position for optical applications. The ultraviolet cutoff of certain compositions in the aluminum borophosphate system occurs at about 190nm provided that special preparation techniques are used to ensure that low impurity levels are maintained. Thus, the new glasses are more transparent at ultraviolet wavelengths than any conventional glasses except fused silica. This feature, coupled with an observed high solubility for rare earth modifiers (which fused silica does not display) and their good solarization resistance, is particularly favorable for luminescent and discharge lamp applications. The aluminum borophosphate glasses also show unusual capabilities for independent property control. For instance, the isoproperty contour lines for refractive index and thermal expansion coefficient are not parallel in a large area of the low phosphate glass-forming region. This means, for example, that refractive index can be adjusted while retaining a constant thermal expansion coefficient, which is a particularly favorable feature for applications such as optical fibers. The glasses of this invention have refractive indices between 1.47 and 1.58, densities between 2.1 and 2.7 gm/cm3 and thermal expansion coefficients between about 26 and 55 × 10-7 /° C.
The following examples illustrate the present invention and are not intended to limit the same:
EXAMPLE I
This example illustrates the method of making the aluminum borophosphate glasses of this invention.
The glass compositions as shown in Table I, glass compositions of varying P2 O5, Al2 O3 and B2 O3 content, were made from the reactants shown. The difference between the relative concentrations of the P2 O5, Al2 O3 and B2 O3 in the reactants and the final compositions is due to vaporization losses or solution of alumina from the crucible wall.
The reactants were weighed and blended and melted in a platinum or aluminum oxide crucible at the temperatures and for the times shown in Table I. In some instances, the reactants were calcined between 300° and 950° C.
                                  TABLE I                                 
__________________________________________________________________________
       Batch                               Analyzed Glass                 
       Composition               Melting                                  
                                      Melting                             
                                           Composition                    
Glass  (mole %)  Batch      Crucible                                      
                                 Temp.                                    
                                      Time (mole %)                       
Compositions                                                              
       Al.sub.2 O.sub.3                                                   
           P.sub.2 O.sub.5                                                
              B.sub.2 O.sub.3                                             
                 Oxides used                                              
                            Material                                      
                                 (° C)                             
                                      (hr.)                               
                                           Al.sub.2 O.sub.3               
                                               P.sub.2 O.sub.5            
                                                  B.sub.2 O.sub.3         
__________________________________________________________________________
1      31.4                                                               
           16.1                                                           
              52.5                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlPO.sub.4            
                            Pt   1610 2    33.6                           
                                               16.1                       
                                                  50.3                    
2      34.3                                                               
            9.2                                                           
              56.5                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlPO.sub.4            
                            Pt   1610 2    35.4                           
                                               10.4                       
                                                  54.2                    
3      38.1                                                               
            6.1                                                           
              55.8                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlPO.sub.4            
                            Pt   1610 2    40.2                           
                                               4.2                        
                                                  55.6                    
4      35.0                                                               
           13.0                                                           
              52.0                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, BPO.sub.4             
                            Pt   1600 2    39.3                           
                                               13.2                       
                                                  47.5                    
5      39.6                                                               
           10.1                                                           
              50.3                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlP.sub.3 O.sub.9     
                            Pt   1600 2    42.8                           
                                               10.4                       
                                                  46.8                    
6      38.0                                                               
           10.0                                                           
              52.0                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, BPO.sub.4             
                            Pt   1605 2    46.6                           
                                               7.0                        
                                                  46.4                    
7      42.1                                                               
           16.8                                                           
              41.1                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlPO.sub.4            
                            Pt   1610 2    47.2                           
                                               16.0                       
                                                  36.8                    
8      44.7                                                               
           15.0                                                           
              40.3                                                        
                 Al.sub.2 O.sub. 3, B.sub.2 O.sub.3, BPO.sub.4            
                            Pt   1605 2    52.2                           
                                               12.3                       
                                                  35.5                    
9      48.5                                                               
            6.3                                                           
              45.2                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, BPO.sub.4             
                            Pt/.4 Rh                                      
                                 1755 0.5  53.0                           
                                                8.9                       
                                                  38.1                    
10     37.9                                                               
           20.4                                                           
              41.7                                                        
                 Al.sub.2 O.sub.3, B.sub.2 O.sub.3, AlPO.sub.4            
                            Al.sub.2 O.sub.3                              
                                 1700 0.5  62.9                           
                                               15.9                       
                                                  21.2                    
__________________________________________________________________________
The glass compositions set forth in Table I were determined to have the properties shown in Table II.
                                  TABLE II                                
__________________________________________________________________________
       Glass                   Thermal                                    
       Transition   Optical    Expansion                                  
Glass  Temperature                                                        
              Refractive                                                  
                    Dispersion                                            
                          Density                                         
                               Coefficient                                
Compositions                                                              
       T.sub.g (° C)                                               
              Index (ν-number)                                         
                          (g/cm.sup.3)                                    
                               (×10.sup.-7 /° C)             
__________________________________________________________________________
1      630    1.475 61    2.145                                           
                               36                                         
2      635    1.503 63    2.280                                           
                               40                                         
3      665    1.532 50    2.394                                           
                               42                                         
4      635    1.506 58    2.320                                           
                               37                                         
5      655    1.532 63    2.392                                           
                               42                                         
6      660    1.528 64    2.416                                           
                               40                                         
7      665    1.512 64    2.358                                           
                               27                                         
8      680    1.530 62    2.458                                           
                               38                                         
9      745    1.573 --    2.623                                           
                               53                                         
10     765    1.541 --    2.561                                           
                               36                                         
__________________________________________________________________________
EXAMPLE II
This example illustrates the method of making the aluminum borophosphate glasses of this invention containing oxide modifiers.
The modified glass compositions were made by the method described in Example I except that they include modifying oxides. The reactants, modifiers, melt temperature and time of heating are shown in Table III.
                                  TABLE III                               
__________________________________________________________________________
     Base Glass Batch                     Analyzed Glass                  
Glass                                                                     
     Composition                Melting                                   
                                     Melting                              
                                          Composition                     
Compo-                                                                    
     (Mole %)  Modifier                                                   
                      Batch Oxides used                                   
                                Temp.                                     
                                     Time (Mole %)                        
sition                                                                    
     Al.sub.2 O.sub.3                                                     
         P.sub.2 O .sub.5                                                 
            B.sub.2 O.sub.3                                               
               (Mole %)                                                   
                      in Base Glass                                       
                                (° C)                              
                                     (hrs.)                               
                                          Al.sub.2 O.sub.3                
                                              P.sub.2 O.sub.5             
                                                 B.sub.2 O.sub.3          
                                                    Modifier              
__________________________________________________________________________
11   42.9                                                                 
         14.3                                                             
            38.1                                                          
               4.7-SiO.sub.2                                              
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1600sub.4                                 
                                     1.5  47.7                            
                                              13.7                        
                                                 34.4                     
                                                    4.2-SiO.sub.2         
12   42.8                                                                 
         14.3                                                             
            37.9                                                          
               5.0-ZrO.sub.2                                              
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1600.sub.4                                
                                     1    42.0                            
                                              17.7                        
                                                 35.2                     
                                                    5.1-ZrO.sub.2         
13   34.0                                                                 
         8.5                                                              
            42.5                                                          
               15.0-ZrO.sub.2                                             
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1590.sub.4                                
                                     1    38.1                            
                                              8.4                         
                                                 37.4                     
                                                    16.1-ZrO.sub.2        
14   27.1                                                                 
         9.0                                                              
            24.0                                                          
               39.9-MgO                                                   
                      Al.sub.2 O.sub.3, B.sub.2 O.sub. 3,                 
                                1610sub.4                                 
                                     2    29.9                            
                                              8.7                         
                                                 22.4                     
                                                    39.0-MgO              
15   38.1                                                                 
         9.5                                                              
            47.5                                                          
               5.0-MgO                                                    
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1610sub.4                                 
                                     2    41.1                            
                                              10.1                        
                                                 43.5                     
                                                    5.3-MgO               
16   24.0                                                                 
         6.0                                                              
            30.0                                                          
               40.0-CdO                                                   
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1620sub.4                                 
                                     2    36.7                            
                                              7.0                         
                                                 25.6                     
                                                    30.7-CdO              
17   24.1                                                                 
         6.0                                                              
            30.1                                                          
               39.8-ZnO                                                   
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1610sub.4                                 
                                     1.5  24.7                            
                                              9.2                         
                                                 27.2                     
                                                    38.9-ZnO              
18   38.1                                                                 
         9.5                                                              
            47.5                                                          
               4.9-SnO.sub.2                                              
                      Al.sub.2 O.sub.3,B.sub.2 O.sub.3,BPO.sub.4          
                                1615 2    42.9                            
                                              10.3                        
                                                 43.4                     
                                                    3.3-SnO.sub.2         
19   38.1                                                                 
         9.5                                                              
            47.5                                                          
               5.0-Na.sub.2 CO.sub.3                                      
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1600sub.4                                 
                                     1    39.9                            
                                              10.6                        
                                                 42.3                     
                                                    7.3-Na.sub.2 O        
20   32.2                                                                 
         8.0                                                              
            40.1                                                          
               19.7-Na.sub.2 CO.sub.3                                     
                      Al.sub.2 O.sub.3, B.sub.2 O.sub.3,                  
                                1600sub.4                                 
                                     1    36.4                            
                                              7.6                         
                                                 34.5                     
                                                    21.4-Na.sub.2         
__________________________________________________________________________
                                                    O                     
The glass compositions set forth in Table III were determined to have the properties set forth in Table IV.
                                  TABLE IV                                
__________________________________________________________________________
       Glass                         Thermal                              
       Transition                                                         
              Resistivity Optical    Expansion                            
Glass  Temperature                                                        
              (ohm-cm)                                                    
                    Refractive                                            
                          Dispersion                                      
                                Density                                   
                                     Coefficient                          
Composition                                                               
       T.sub.g (° C)                                               
              at 25° C                                             
                    Index (ν-number)                                   
                                (g/cm.sup.3)                              
                                     (×10.sup.-7 /° C)       
__________________________________________________________________________
11     710    --    1.532 62    2.456                                     
                                     37                                   
12     680    --    1.542 60    2.525                                     
                                     36                                   
13     705    --    1.601 53    2.791                                     
                                     42                                   
14     695    --    1.544 65    2.534                                     
                                     44                                   
15     670    --    1.541 62    2.462                                     
                                     44                                   
16     635    --    1.594 32    3.219                                     
                                     51                                   
17     620    --    1.615 41    3.182                                     
                                     48                                   
18     675    --    1.548 53    2.544                                     
                                     42                                   
19     615    3 × 10.sup.19                                         
                    1.523 61    2.399                                     
                                     48                                   
20     495    2 × 10.sup.13                                         
                    1.515 70    2.405                                     
                                     75                                   
__________________________________________________________________________

Claims (4)

We claim:
1. An aluminum borophosphate glass composition comprising 2 to 18 mole percent P2 O5, 30 to 70 mole percent Al2 O3 and 20 to 60 mole percent B2 O3.
2. An aluminum borophosphate glass composition of from 2 to 18 mole percent P2 O5, 30 to 70 mole percent Al2 O3, and 20 to 60 mole percent B2 O3 ; further containing up to about 35 weight percent of a rare earth oxide, said percent of a rare earth oxide based upon the weight of said aluminum borophosphate glass.
3. An aluminum borophosphate glass composition of from 2 to 18 mole percent P2 O5, 30 to 70 mole percent Al2 O3, and 20 to 60 mole percent B2 O3 ; further containing up to 20 mole percent ZrO2, said percent ZrO2 based upon the total glass composition, said glass composition being characterized by increased glass transition temperature.
4. The glass composition of claim 2 wherein said rare earth oxide is selected from the group consisting of neodymium oxide, terbium oxide, and europium oxide.
US05/773,525 1977-03-02 1977-03-02 Aluminum borophosphate glass compositions Expired - Lifetime US4127415A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US05/773,525 US4127415A (en) 1977-03-02 1977-03-02 Aluminum borophosphate glass compositions
GB7567/78A GB1593232A (en) 1977-03-02 1978-02-24 Aluminium borophosphate glass compositions
DE19782808647 DE2808647A1 (en) 1977-03-02 1978-02-28 ALUMINUM BOROPHOSPHATE GLASS COMPOSITIONS
CA297,993A CA1101895A (en) 1977-03-02 1978-03-01 Aluminum borophosphate glass compositions
JP2288478A JPS53109513A (en) 1977-03-02 1978-03-02 Aluminium borophosphate glass compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US05/773,525 US4127415A (en) 1977-03-02 1977-03-02 Aluminum borophosphate glass compositions

Publications (1)

Publication Number Publication Date
US4127415A true US4127415A (en) 1978-11-28

Family

ID=25098559

Family Applications (1)

Application Number Title Priority Date Filing Date
US05/773,525 Expired - Lifetime US4127415A (en) 1977-03-02 1977-03-02 Aluminum borophosphate glass compositions

Country Status (5)

Country Link
US (1) US4127415A (en)
JP (1) JPS53109513A (en)
CA (1) CA1101895A (en)
DE (1) DE2808647A1 (en)
GB (1) GB1593232A (en)

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302074A (en) * 1979-04-02 1981-11-24 Bell Telephone Laboratories, Incorporated Aluminum metaphosphate optical fibers
US4366253A (en) * 1979-08-10 1982-12-28 Fuji Photo Film Co., Ltd. Phosphate glass compositions, and glass-ceramic materials, and methods of making the same
US4379616A (en) * 1979-04-02 1983-04-12 Bell Telephone Laboratories, Incorporated Aluminum metaphosphate optical fibers
US4633366A (en) * 1985-08-07 1986-12-30 Sprague Electric Company Laminar electrical component with magnesium orthoborate
US5106532A (en) * 1990-05-14 1992-04-21 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor
US5116532A (en) * 1990-05-14 1992-05-26 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor
US5132042A (en) * 1990-05-14 1992-07-21 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor with improved brightness
US5154852A (en) * 1991-11-18 1992-10-13 Gte Products Corporation Method of making lanthanum cerium terbium gadolinium phosphate phosphor
US5488016A (en) * 1990-12-20 1996-01-30 Corning Incorporated Cellulated bodies produced from phosphorous polymers
US6484539B1 (en) * 1996-01-11 2002-11-26 Containerless Research, Inc. Glass fiber having compositions of alumina-lanthana and made from undercooled molten materials
CN109942201A (en) * 2019-04-25 2019-06-28 济南大学 A kind of titania additive phosphate alkali-resistant glass fibre and preparation method thereof
CN110228948A (en) * 2019-05-14 2019-09-13 重庆邮电大学 A kind of novel photoluminescent transparent glass ceramics and preparation method thereof
US11247934B2 (en) 2018-01-16 2022-02-15 Corning Incorporated Optical boroaluminate glasses

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63282140A (en) * 1987-05-11 1988-11-18 Kuraray Co Ltd Crystallized glass
EP2468690B1 (en) * 2010-12-23 2015-04-22 Centre National de la Recherche Scientifique (CNRS) Luminophore composition for UV-visible light conversion and light converter obtained therefrom

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1964629A (en) * 1930-09-19 1934-06-26 Ig Farbenindustrie Ag Vitreous composition
US2486812A (en) * 1941-01-27 1949-11-01 Monsanto Chemicals Ceramic bodies
US3248234A (en) * 1955-02-12 1966-04-26 Saint Gobain Glass compositions

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1964629A (en) * 1930-09-19 1934-06-26 Ig Farbenindustrie Ag Vitreous composition
US2486812A (en) * 1941-01-27 1949-11-01 Monsanto Chemicals Ceramic bodies
US3248234A (en) * 1955-02-12 1966-04-26 Saint Gobain Glass compositions

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
Volf-Technical Glasses, pp. 401-402, SNTL Publishers, Prague and Sir Isaac Pitman, London (1961). *

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4302074A (en) * 1979-04-02 1981-11-24 Bell Telephone Laboratories, Incorporated Aluminum metaphosphate optical fibers
US4379616A (en) * 1979-04-02 1983-04-12 Bell Telephone Laboratories, Incorporated Aluminum metaphosphate optical fibers
US4366253A (en) * 1979-08-10 1982-12-28 Fuji Photo Film Co., Ltd. Phosphate glass compositions, and glass-ceramic materials, and methods of making the same
US4633366A (en) * 1985-08-07 1986-12-30 Sprague Electric Company Laminar electrical component with magnesium orthoborate
US5132042A (en) * 1990-05-14 1992-07-21 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor with improved brightness
US5116532A (en) * 1990-05-14 1992-05-26 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor
US5106532A (en) * 1990-05-14 1992-04-21 Gte Products Corporation Method of making lanthanum cerium terbium phosphate phosphor
US5488016A (en) * 1990-12-20 1996-01-30 Corning Incorporated Cellulated bodies produced from phosphorous polymers
US5154852A (en) * 1991-11-18 1992-10-13 Gte Products Corporation Method of making lanthanum cerium terbium gadolinium phosphate phosphor
US6484539B1 (en) * 1996-01-11 2002-11-26 Containerless Research, Inc. Glass fiber having compositions of alumina-lanthana and made from undercooled molten materials
US11247934B2 (en) 2018-01-16 2022-02-15 Corning Incorporated Optical boroaluminate glasses
CN109942201A (en) * 2019-04-25 2019-06-28 济南大学 A kind of titania additive phosphate alkali-resistant glass fibre and preparation method thereof
CN109942201B (en) * 2019-04-25 2021-10-22 济南大学 Titanium dioxide doped phosphate alkali-resistant glass fiber and preparation method thereof
CN110228948A (en) * 2019-05-14 2019-09-13 重庆邮电大学 A kind of novel photoluminescent transparent glass ceramics and preparation method thereof

Also Published As

Publication number Publication date
JPS53109513A (en) 1978-09-25
DE2808647A1 (en) 1978-09-07
GB1593232A (en) 1981-07-15
CA1101895A (en) 1981-05-26

Similar Documents

Publication Publication Date Title
US4127415A (en) Aluminum borophosphate glass compositions
US5591682A (en) Low expansion transparent glass-ceramic
US4768859A (en) Cladding glass for optical fiber
TW483875B (en) Transparent apatite glass ceramics
JP2001048572A (en) Neodium glass for envelope and filter of tungsten- halogen lamp
US4409337A (en) Glass envelopes for tungsten-halogen lamps
JP4671647B2 (en) Optical glass with small photoelastic constant
EP0048120B1 (en) Glass envelopes for tungsten-halogen lamps and production thereof
US4343908A (en) Optical glass having nD =1.63±(1.5×10-2), vD =59.5±1.0 with a high chemical stability and a low tendency to crystallization
JP2002137935A (en) Glass for fluorescent lamp, glass tube for fluorescent lamp and fluorescent lamp
JPH10297933A (en) Glass for faraday rotator
JPH07121814B2 (en) Topped quartz glass
US4394453A (en) Envelopes for tungsten-halogen lamps
WO2003072518A1 (en) Optical glass
JPS61215233A (en) Silicophosphate laser glass
JPS63156038A (en) Glass for cathode ray tube face plate
EP0218135A2 (en) Silica and boron-containing ultraphosphate laser glass with low concentration quenching and improved thermal shock resistance
US4576920A (en) B2 O3 --P2 O5 --SiO2 glass-ceramics
EP0105670B1 (en) Lead aluminoborofluorosilicate moldable glasses
US4323654A (en) Moldable glass compositions
JPH033620B2 (en)
JPH03218940A (en) Ultraviolet transmitting glass
CA2312702A1 (en) Rare earth element-halide environments in oxyhalide glasses
JPH02293346A (en) Glass for optical fiber
JPS6316348B2 (en)